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Many pharmaceuticals (e.g. antibiotics, contrast media, beta blockers) are excreted unmetabolized and enter wastewater treatment plants (WWTPs) through the domestic sewage system. Research has shown that many of them are not effectively removed by conventional wastewater treatment and therefore are detected in surface waters. Reverse osmosis (RO) is one of the most effective means for removing a wide range of micropollutants in water recycling. However, one significant disadvantage is the need to dispose the resultant RO concentrate. Due to the fact that there are elevated concentrations of micropollutants in the concentrate, a direct disposal to surface water could be hazardous to aquatic organisms. As a consequence, further treatment of the concentrate is necessary. In this study, ozonation was investigated as a possible treatment option for RO concentrates. Concentrate samples were obtained from a RO-membrane system which uses municipal WWTP effluents as feeding water to produce infiltration water for artificial groundwater recharge. In this study it could be shown that ozonation is efficient in the attenuation of selected pharmaceuticals, even in samples with high TOC levels (46 mg C/L). Tests with chlorinated and non-chlorinated WWTP effluent showed an increase of ozone stability, but a decrease of hydroxyl radical exposure in the samples after chlorination. This may shift the oxidation processes towards direct ozone reactions and favors the degradation of compounds with high apparent second order rate constants. Additionally it might inhibit an oxidation of compound predominantly reacting with OH radicals. Ozone reaction kinetics were investigated for beta blockers (acebutolol, atenolol, metoprolol and propranolol) which are permanently present in WWTP effluents. For beta blockers two moieties are common which are reactive towards ozone, a secondary amine group and an activated aromatic ring. The secondary amine is responsible for a pH dependence of the direct ozone reaction rate, since only the deprotonated amine reacts very quickly. At pH 7 acebutolol, atenolol and metoprolol reacted with ozone with an apparent second order rate constant of about 2000 M-1 s-1, whereas propranolol reacted at ~1.0 105 M-1 s-1. The rate constants for the reaction of the selected compounds with OH radicals were determined to be 0.5-1.0 x 1010 M-1 s-1. Oxidation products (OPs) formed during ozonation of metoprolol and propranolol were identified via liquid chromatography (LC) tandem mass spectrometry. Ozonation led to a high number of OPs being formed. Experiments were carried out in MilliQ-water at pH 3 and pH 8 as well as with and without the radical scavenger tertiary butanol (t-BuOH). This revealed the influence of pH and the OH radical exposure on OP formation. The OH radical exposure was determined by adding the probe compound para-chlorobenzoic acid (pCBA). Metoprolol: To define the impacts of the protonated and non protonated metoprolol species on OH radical formation, the measured pCBA attenuation was compared to modeled values obtained by a simplified kinetic model (Acuchem). A better agreement with the measured results was obtained, when the model was based on a stoichiometric formation of OH radical precursors (O2-) during the primary ozone reaction of metoprolol. However, for reaction of a deprotonated molecule (attack of the aromatic ring) a formation of O2- could be confirmed, but an assumed stoichiometric O2- formation over-estimated the formation of OH radicals in the system. Analysis of ozonated raw wastewater and municipal WWTP effluent spiked with 10 μM metoprolol exhibited a similar OP formation pattern as detected in the reaction system at pH 8 without adding radical scavenger. This indicated a significant impact of OH radical exposure on the formation of OPs in real wastewater matrices. Propranolol: The primary ozonation product of propranolol (OP-291) was formed by an ozone attack of the naphthalene ring, which resulted in a ring opening and two aldehyde moieties being formed. OP-291 was further oxidized to OP-307, presumably by an OH radical attack, which was then further oxidized to OP-281. Reaction pathways via ozone as well as OH radicals were proposed and confirmed by the chemical structures identified with MS2 and MS3 data. It can be concluded that ozonation of WWTP effluent results in the formation of a high number of OPs with an elevated toxic potential (i.e. formation of aldehydes).
The genus Cheilolejeunea (Spruce) Schiffn. (Lejeuneaceae, Jungermanniopsida) is represented by 23 species in continental tropical Africa. The morphological characters such as features of the stem, leaf, lobule and perianth traditionally used to separate the taxa at both species and generic level have been found to be unstable. The species are variably ranked in several subgenera including Cheilolejeunea (Spruce) Schiffn., Euosmolejeunea Schiffn., Strepsilejeunea (Spruce) Schiffn. and Xenolejeunea Kachroo & Schust. Although the genus has never been monographed, there are a few regional taxonomic accounts for America, Australia and China. A comprehensive revision of Cheilolejeunea species is lacking in Africa where the existing studies are based on single subgenus and sub-regional flora or checklist compilations, which are sometimes without identification keys. This study revises the taxonomy of Cheilolejeunea and the closely allied genus Leucolejeunea A. Evans, in continental Africa based on morphological data analysed using phenetic and phylogenetic methods.
Diese Arbeit untersucht die Biozönosen kontaminierter schlammig-schluffiger Sedimente in Stillwasserzonen großer Flüsse. Diese feinkörnigen und weichgründigen Sedimente beherbergen Lebensgemeinschaften, die zu einem großen Teil als Meiozoobenthos angesprochen werden und im Vergleich zu den Makrozoobenthos-Biozönosen grobkörniger und hartgründiger Fließgewässer und den Meiobenthos-Biozönosen der Küsten-, Tiden- und Ästuarbereiche bisher nur unzulänglich untersucht worden sind. Da die feinkörnigen Sedimente eine große Kapazität zur Schadstoffbindung haben, sind sie generell von großem ökotoxikologischen und wasserbaulichen Interesse. Ziele der Arbeit: (1) Entwicklung einer quantitativen Methode zur Bestandserfassung. (2) Untersuchung der lokalen und saisonalen Dynamik der benthischen Metazoen- Biozönose in Schluffsedimenten. (3) Ermittlung der Einflüsse chemischer und physikalischer Sedimenteigenschaftenrnauf die Biozönosen. (4) Beschreibung der Resilienz der Benthos-Biozönosen schluffiger Sedimente; Einfluss katastrophaler Ereignisse.
Small headwater streams comprise most of the total channel length and catchment area in fluvial networks. They are tightly connected to their catchments and, thus, are highly vulnerable to changes in catchment hydrologic budgets and land use. Although these small, often fishless streams are of little economic interest, they are vital for the ecological and chemical state of larger water bodies. Although numerous studies investigate the impact of various anthropogenic stressors or altered catchment conditions, we lack an in-depth understanding of the natural conditions and processes in headwater streams. This natural state, however, largely affects how a headwater stream responds to anthropogenic or climatic changes. One of the major threats to aquatic ecosystems is the excessive anthropogenic input of nutrients leading to eutrophication. Nutrients exert a bottom-up effect in the food web, foremost affecting primary producers and their consumers, i.e. periphyton and benthic grazers in headwater streams. The periphyton-grazer link is the main path of autochthonous (in-stream) production into the stream food web and the strength of this link largely determines the effectiveness of this pathway. Therefore, this thesis aims at elucidating important biological processes with the explicit focus on periphyton-grazer interactions. I assessed different aspects of periphyton-grazer interactions using laboratory experiments to solve methodological problems, and using a field study to compare the benthic communities of three morphologically similar, phosphorus-limited, near-natural headwater streams. With the results of the laboratory experiments, I was able to show that periphyton RNA/DNA ratios can be used as proxy for periphyton growth rates in controlled experiments and that the fatty acid composition of grazing mayfly nymphs responds to changes in fatty acids provided by the diet after only two weeks. The use of the RNA/DNA ratio as a proxy for periphyton growth rate allows a comparison of these growth rates even in simple experimental set-ups and thereby permits the inclusion of this important process in ecotoxicological or ecological experiments. The observed fast turnover rates of fatty acids in consumer tissues show that even short-term changes in available primary producers can alter the fatty acid composition of primary consumers with important implications for the supply of higher trophic levels with physiologically important polyunsaturated fatty acids. With the results of the field study, I revealed gaps in the understanding of the linkages between catchment and in-stream phosphorus availability under near-natural conditions and demonstrated that seemingly comparable headwater streams had significantly different benthic communities. These differences most likely affect stream responses to environmental changes.
Dracaena L. (Ruscaceae) is a predominantly African genus with a smaller centre of diversity in South-East Asia. The taxonomy of the 29 species occurring in Central, East and Southern Africa was revised through phenetic and phylogenetic analyses of the morphology as well as through herbarium, literature and field studies. An infrageneric classification is proposed, in which four sub-genera are recognised for the first time. A taxonomic account for the study area incorporating an identification key, distribution maps and an IUCN Red List assessment is presented. Analysis of Dracaena phytogeography reveals that the Guineo-Congolian centre of endemism is the richest with 21 species while the Maputaland-Pondoland regional mosaic and the Guinea-Congolia/Sudania regional transition zone are the poorest, having only one species each. Investigation of the ecology of Dracaena in the Kakamega Forest, Kenya, shows that it plays an important role in the forest ecology and is an indicator of forest quality.
Estuaries are characterized by a longitudinal salinity gradient. This gradient is one of the main environmental factors responsible for the distribution of organisms. Distinguishing salinity zones is of crucial importance, e.g., for the development of tools for the assessment of ecological quality. The methods most often applied for classifying water according to salinity are the Venice System and the method of Bulger et al. (1993), both of which determine zone boundaries using species occurrences relative to mean salinity. However, although these methods were developed for homoiohaline waters, they have also been routinely applied to poikilohaline systems. I tested the applicability of both methods using salinity and macroinvertebrate data for the poikilohaline Elbe Estuary (Germany). My results showed that the mid-estuary distribution of macro-invertebrates is determined by variation in salinity rather than by mean salinity. Consequently, neither of the two methods is applicable for defining salinity zones in the Elbe Estuary. Cluster analysis combined with a significance test, by contrast, was a better tool for identifying the boundaries of salinity zones in poikilohaline systems.
In many estuaries, such as the Elbe Estuary, a maximum turbidity zone (MTZ) develops, where suspended matter accumulates owing to circulation processes. It is assumed that the MTZ is a stressful environment with an excess of organic matter, high deposition rates, large variations in salinity, and dredging activities. Under such harsh conditions, populations might remain below the carrying capacity, and it is assumed that competition is of little importance, as predicted by the stress gradient hypothesis. I tested whether competition for food is important in the MTZ of the Elbe Estuary using stable isotope analysis of the macroinvertebrate community. The isotopic niches of no two taxa within a feeding group overlapped, which indicated different resource use and the absence of competition. The main reasons for the lack of overlap of isotopic niches were differences in habitat, feeding behavior, and migration behavior.
The Elbe Estuary is nowadays highly industrialized and has long been subjected to a plethora of human-caused alterations. However, it is largely unknown what changes occurred in benthic communities in the last century. Hence, I considered taxonomic and functional aspects of macrobenthic invertebrates of the Elbe Estuary given in data from 1889 (most natural state), 1985 and 1986 (highly polluted state), and 2006 (recent state) to assess benthic community shifts. Beta-diversity analysis showed that taxonomic differences between the sampling dates were mainly due to species turnover, whereas functional differences were predominantly a result of functional nestedness. Species number (S), functional richness (FRic), and functional redundancy reached minimum values in 1985 and 1986 and were highest and rather similar in 1889 and 2006. The decline in FRic from 1889 to 1985/1986 was non-random, consistent with habitat filtering. FRic, functional beta diversity, and S data suggested that the state of the estuary from 1889 was almost re-established in 2006. However, the community in 1889 significantly differed from that in 2006 owing to species replacement. My results indicate that FRic and FR in 1889 could have promoted ecosystem resilience and stability.